In the 19th century a German scientist, R. Wolffenstein, discovered acetone peroxide using an inorganic acid as a catalyst and received a patent on its use as an explosive. Acetone peroxide is noted for its instability and thus, for more than 100 years was not used militarily or commercially. However, in the 21st century man's evil twin has embraced acetone peroxide as a weapon of choice for terrorist activities and suicide bombers.
Triacetone triperoxide (TATP) and other explosives of the peroxide family are used extensively by terrorist organizations around the world because they are easy to prepare and very difficult to detect. TATP can be made from common household items such as drain cleaner (sulfuric acid —H2SO4), hydrogen peroxide (H2O2), and acetone (CH3COCH3), a nail polish remover and common organic solvent. The low cost of the reactants and the ease with which they can be obtained lead to the manufacture of TATP by those without the resources to manufacture or buy more sophisticated explosives.
The acid-catalyzed peroxidation of acetone produces a mixture of dimeric and trimeric forms. The trimer is the more stable form, but not much more so than the dimer. All forms of acetone peroxide are insoluble in water and very sensitive to initiation. Organic peroxides are sensitive, dangerous explosives. The military does not use them because there are many better alternatives. For people who synthesize homemade explosives, there are far safer alternatives. Even nitroglycerin is not as sensitive as acetone peroxide. TATP is highly unstable and sensitive to heat and friction and is well deserving of the nickname, “Mother of Satan.”
Global security, travel, human and animal life are threatened. The world population is at increased risk of adverse outcomes, including constant fear, terror and death.
As an illustration of the gravity of the situation, on Dec. 22, 2001, American Airlines Flight 53, carrying a crew of 14 and a passenger complement of 184, including “shoe bomber” Richard Reid, departed Charles de Gaulle Airport in Paris, France, bound for Miami, Fla. Approximately one and a half hours into the flight, a flight attendant smelled what she thought was a burnt match. After the flight attendant determined that it was coming from where Reid was seated, she confronted Reid, at which time he put a match into his mouth. The flight attendant alerted the captain over the intercom system. Reid went on to light another match in an apparent attempt to set fire to his shoe. The flight attendant then noticed a wire protruding from the shoe. A struggle ensued among several of the flight attendants, passengers and Reid. Ultimately Reid was subdued and restrained for the remainder of the flight. The flight was diverted for landing to Boston's Logan International Airport where Reid was taken into federal custody. Later, analysis by the FBI laboratory in Washington determined that there were two functional improvised explosive devices hidden in Reid's shoes made of the explosive material triacetone triperoxide, known as “TATP,” and other components. Richard Reid's shoe had 8 or 10 ounces of triacetone triperoxide and PETN, a high grade military plastic explosive.
The instability of triacetone triperoxide, as mentioned earlier, makes the remediation of a contaminated area a challenging problem. Thus, the best solution is to use a methodology wherein the TATP is degraded in place, to the point where it is safe to remove and/or that it is completely degraded. Such a methodology would have global demand and could be used to abate the crises caused by “shoe bombers” on airplanes or “suicide bombers” in hotels, restaurants or on the streets.
The following US Patents are related to degradation or removal of deleterious materials, including explosives.
U.S. Pat. No. 4,641,566 to Pomeroy teaches an in situ method for detecting buried land mines by non-destructive means involving the spraying of a suspected area with a leach of ionized metal and leaching the ionized metal into the soil to leave a metallic concentrate on an impervious object, such as a plastic mine; then, scanning the area with a metal detector.
U.S. Pat. No. 4,908,323 to Werner discloses a method for determining organic peroxides in aqueous and organic solutions using a peroxide detecting amount of a titanium (IV) compound.
U.S. Pat. No. 5,434,336 to Adams et al. describes an in situ process for the destruction of explosives by heating in the presence of elemental sulfur at temperatures below their spontaneous decomposition temperatures.
U.S. Pat. No. 6,664,298 to Reinhart et al. describes the in situ use of a zero-valent metal emulsion to dehalogenate solvents, such as, trichloroethylene (TCE) and other halogentated hydrocarbons that contaminate ground water and soil environments. The preferred zero-valent metal particles are nanoscale and microscale iron particles. U.S. Pat. No. 6,767,717 to Itzhaky et al. describes a method of detecting a peroxide-based explosive in a sample suspected of having such an explosive; the method includes dissolving the sample in an organic solvent, then contacting the solution with an aqueous solution of a strong acid capable of decomposing the explosive to release hydrogen peroxide, and further contacting the mixture with a peroxidase enzyme to produce a pronounced change in the color of the substrate or its color intensity.
U.S. Pat. No. 6,773,674 to Bannister et al. describes methods and systems for detecting the presence of an energetic material, such as triacetone triperoxide (TATP), in a sample which is known to have the energetic material using thermal analysis for detecting and identifying explosives and other controlled substances. This method requires moving the explosive materials to a laboratory with appropriate analytical equipment.
U.S. Pat. No. 7,077,044 to Badger et al. discloses a method for bioremediating undetonated explosive devices by mixing an explosive mixture with microorganisms.
U.S. Pat. No. 7,159,463 to Dayagi et al. discloses a sensitive and selective method and device for the detection of trace amounts of a substance. A piezoelectric crystal element is used in a sensor device for identifying at least one foreign material from the environment.
WO1999/043846 to Keinan et al. discloses a method and kit for the detection of explosives. The method relies on the decomposition of TATP in the presence of concentrated aqueous sulfuric acid to produce hydrogen peroxide, which is detected by horseradish peroxidase and a color-change reagent.
J. A. Bellamy in J. Forensic Science 1999, 44(3), 603-608 reports that solutions of TATP in acetone and other organic solvents have been known to detonate, although solutions in toluene appear to be somewhat stable. It is therefore a risky proposition to dissolve the explosive in organic solvent in an attempt to remove it if no remediaton step is involved.
Irradiation with UV light has been used as a method of decomposing TATP in a detection scheme involving horseradish peroxidase/indicator combination as reported by R. Shulte-Ladbeck, et al. in “Trace Analysis of Peroxide-Based Explosives” Analytical Chemistry 2003, 75, 731-735.
The thermal decomposition of TATP has been found to have an activation energy which is within the reasonable expectation for a unimolecular decomposition initiated by a peroxide bond homolysis according to J. C. Oxley et al. in “Decomposition of a Multi-Peroxidic Compound Triacetone Triperoxide (TATP)” Propellants, Explosives, Pyrotechnics, 2002, 27, 209-216. Thermal decomposition of TATP in refluxing toluene has been found to be a slow process as reported by N. A. Milas et al. in “Studies in Organic Peroxides XXIV. Preparation, Separation and Identification of Peroxides Derived from Diethyl Ketone and Hydrogen Peroxide.” J. Am. Chem. Soc. 1959, 82, 3361-3364.
The complexation of TATP with ions was investigated by F. Dubnikova, et al. and many ions are calculated to form stable complexes with the explosive, as reported in “Novel Approach to the Detection of Triacetone Triperoxide (TATP): Its Structure and Its Complexes with Ions” J. Phys. Chem. A2002, 106, 4951-4956.
Further research is available on the use of nano-size elemental metal particles, such as, iron in emulsion systems capable of degrading chlorinated hydrocarbons in a controlled manner, the use of nanometal particles in emulsion systems where the reductive reactions take place within an emulsion droplet and where the hydrophilic and hydrophobic properties of the skin of the droplet can be controlled to a level so as to facilitate the entrance of the molecule of choice that is to be degraded. See C. L. Geiger, et al. “Nanoscale and Microscale Iron Emulsions for Treating DNAPL.” in: Innovative Strategies for the Remediation of Chlorinated Solvents and DNAPL in the Subsurface. Series 837, 2002, ACS Books, Washington D.C. Jacqueline Quinn, et al. “Evaluating The Distribution Of Emulsified Zero-Valent Iron For Four Different Injection Techniques,” Remediation of Chlorinated and Recalcitrant Compounds 2004, May 2004. Battelle Press, ISBN #1-57477-132-9. Jacqueline Quinn, et al. “Field Demonstration of DNAPL Dehalogenation Using Emulsified Zero-Valent Iron,” 2005, Environ. Sci. Technol. 2005; 39(5); 1309-1318.
Kristen Milum, et al. in “In Situ Heavy Metal Contaminant Removal Using Emulsified Iron,” Remediation of Chlorinated and Recalcitrant Compounds 2004, May 2004. Battelle Press, ISBN #1-57477-132-9 discuss various complexing agents that can be added along with nano-size metal particles into the emulsion system.
Collectively, the above references do not provide a composition of matter and in situ methodologies that safely degrade triacetone triperoxide (TATP) and other organic peroxides that are “homemade” weapons of choice used by 21st century terrorists and extremists. There is a great need for a composition and method that provides safe and effective means for in situ degradation of explosive materials; the present state of the art does not meet this need.